JP2020026607A - Carbodiimide crosslinking agent for fiber treatment - Google Patents

Abstract

To provide a carbodiimide crosslinking agent for fiber treatment that achieves improved friction fastness in printing at a relatively low temperature.SOLUTION: The present invention provides a carbodiimide crosslinking agent for fiber treatment, comprising a polycarbodiimide composition which is obtained by carbodiimidizing a reaction product of a linear aliphatic diisocyanate and an alcohol, and which is configured such that: the alcohol contains a polyol and a monool; and the carbodiimide equivalent of the polycarbodiimide composition is less than 550 g/mol.SELECTED DRAWING: None

Description

  The present invention relates to a carbodiimide crosslinking agent for treating fibers.

  Conventionally, as a fiber treatment, printing is known in which an ink is prepared by mixing a pigment, a water-dispersible resin, and a crosslinking agent, the ink is printed on a fabric, and then the ink is cured to form an image on the fabric. ing. It has also been proposed to use a carbodiimide composition as a crosslinking agent in fiber treatment.

  The carbodiimide composition is obtained, for example, by reacting dicyclohexylmethane-4,4-diisocyanate with a carbodiimidization reaction, and then reacting the obtained reaction product with polyoxyethylene glycol having a molecular weight of 1,000 and polyoxyethylene glycol. A polycarbodiimide composition has been proposed (for example, see Patent Document 1 (Synthesis Example 5)).

JP 2018-104605 A

  A crosslinking agent for printing is required to obtain fibers having excellent friction fastness (wear resistance) even when printing is performed at a relatively low temperature (for example, 120 ° C. or lower).

  However, when the carbodiimide composition described in Patent Literature 1 is used as a crosslinking agent for printing, there is a problem that the rub fastness of the printing process is not sufficient.

  The present invention is a carbodiimide crosslinking agent for fiber treatment, which can improve the fastness to friction when printing at a relatively low temperature.

  The present invention [1] includes a polycarbodiimide composition including a carbodiimide modified product of a reaction product of a linear aliphatic diisocyanate and an alcohol, wherein the alcohol includes a polyol and a monol, and the polycarbodiimide composition includes: Contains a carbodiimide cross-linking agent for fiber treatment, wherein the carbodiimide equivalent of is less than 550 g / mol.

  The present invention [2] includes the carbodiimide crosslinking agent for fiber treatment according to the above [1], wherein the polyol has a molecular weight of 120 or more and 1000 or less.

  The present invention [3] includes the carbodiimide crosslinking agent for fiber treatment according to the above [1] or [2], wherein the average number of functional groups of the polyol is 2.

  The present invention [4] includes the carbodiimide crosslinking agent for fiber treatment according to any one of [1] to [3], wherein the linear aliphatic diisocyanate is 1,5-pentane diisocyanate. .

  In the present invention [5], in the chromatogram when the polycarbodiimide composition is measured by gel permeation chromatography, the area ratio of the peak area of the polystyrene-equivalent molecular weight of 500 or less to the total peak area is 6.5% or less. The carbodiimide crosslinking agent for fiber treatment according to any one of [1] to [4], wherein an area ratio of a peak area having a molecular weight of 1,000 or less in terms of polystyrene to an entire peak area is 10.0% or less. Contains.

  In the carbodiimide crosslinking agent for fiber treatment of the present invention, a prepolymer is obtained by a reaction between a linear aliphatic diisocyanate and an alcohol containing a polyol, and the prepolymer is carbodiimidated to form a modified carbodiimide having a relatively high molecular weight. can get. As a result, by using the carbodiimide crosslinking agent for fiber treatment, it is possible to improve the fastness to friction when printing at a relatively low temperature (120 ° C. or lower).

FIG. 1 shows a GPC chromatogram of the polycarbodiimide composition obtained in Example 1.

  The carbodiimide crosslinking agent for fiber treatment of the present invention is a crosslinking agent (crosslinking agent for printing) used for printing on fibers or leather. In the following, the carbodiimide crosslinking agent for fiber treatment may be simply referred to as a crosslinking agent.

  The crosslinker comprises a polycarbodiimide composition, preferably the crosslinker comprises a polycarbodiimide composition.

  The polycarbodiimide composition contains, as a main component (for example, at a ratio of 90% by mass or more based on the polycarbodiimide composition), a carbodiimide modified product of a reaction product of a linear aliphatic diisocyanate and an alcohol.

  The modified carbodiimide can be obtained by subjecting a reaction product of a linear aliphatic diisocyanate and an alcohol to a carbodiimidation reaction.

  Examples of the linear aliphatic diisocyanate include ethylene diisocyanate, 1,3-propane diisocyanate, 1,4-butane diisocyanate, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), and 1,6-hexane diisocyanate (hexamethylene diisocyanate). Diisocyanates, HDI) linear aliphatic diisocyanates having 1 to 20 carbon atoms such as 1,8-octane diisocyanate (octamethylene diisocyanate) and 1,12-dodecane diisocyanate (dodecamethylene diisocyanate).

  These linear aliphatic diisocyanates can be used alone or in combination of two or more.

  By using a linear aliphatic diisocyanate, the curability at low temperatures and the fastness to friction can be improved.

  As the linear aliphatic diisocyanate, from the viewpoint of improving low-temperature curability and friction fastness, preferably, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI And more preferably 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI).

  In particular, 1,5-pentane diisocyanate has a smaller number of carbon atoms and a smaller molecular weight than 1,6-hexane diisocyanate, so that when producing a polycarbodiimide composition having the same molecular weight, 1,5-pentane diisocyanate is used. Carbodiimide group concentration in the polycarbodiimide composition can be increased as compared with the case where 1,6-hexanediisocyanate is used. In addition, 1,5-pentanediisocyanate having an odd number of carbon atoms has lower crystallinity due to an amorphous structure derived from an odd number of carbon atoms than 1,6-hexane diisocyanate having an even number of carbon atoms. Excellent dispersibility. As a result, the low-temperature curability and friction fastness can be improved.

  Furthermore, when 1,5-pentamethylene diisocyanate is used, thermal decomposition of the uretonimine group described later is more likely to occur than in the case where 1,6-hexamethylene diisocyanate is used, and therefore, it is possible to obtain a polycarbodiimide composition with a high yield. it can. In addition, since it can be handled even at a low temperature, the increase in the molecular weight of uretonimine can be suppressed.

  The alcohol contains a polyol and a monol, and preferably consists of the polyol and the monol.

  The polyol is an organic compound having two or more hydroxyl groups in a molecule, and includes a monomer polyol and a polymer polyol.

  The monomer polyol is an organic monomer (single compound (hereinafter the same)) having two or more hydroxyl groups in a molecule, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butane Diol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol , 1,14-, tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20-eicosandiol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2 2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C2-20) diol 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2 Dihydric alcohols such as 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol and dipropylene glycol, for example, trihydric alcohols such as glycerin, trimethylolpropane and triisopropanolamine; For example, tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin, for example, pentahydric alcohols such as xylitol, for example, sorbitol, mannitol, allitol, iditol, dalcitol, altitol , Inositol, hexahydric alcohols such as dipentaerythritol, for example, 7-valent alcohols such as perseitol, for example, 8 monohydric alcohol and sucrose.

  These monomer polyols can be used alone or in combination of two or more.

  Preferred examples of the monomer polyol include dihydric alcohols, and more preferred examples include 1,6-hexanediol and 1,10-decanediol.

  The polymer polyol is an organic polymer having two or more hydroxyl groups in a molecule (a polymer compound (the same applies hereinafter)), and examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, and polyolefin. Examples thereof include polyols, acrylic polyols, and vinyl monomer-modified polyols, and preferably include polyether polyols, polyester polyols, and polycarbonate polyols.

  Examples of the polyether polyol include a polyoxyalkylene (C2 to C3) polyol, a polytetramethylene ether polyol, and the like.

  Examples of the polyoxyalkylene (C2 to C3) polyol include addition polymerization of a C2 to C3 alkylene oxide using a monomer polyol or a known monomer (low molecular weight) polyamine as an initiator. Things.

  Examples of the monomer polyol include the above-mentioned monomer polyols, preferably dihydric alcohols and trihydric alcohols, and more preferably dihydric alcohols.

  Examples of the alkylene oxide having 2 to 3 carbon atoms include propylene oxide (1,2-propylene oxide) and ethylene oxide. These alkylene oxides can be used alone or in combination of two or more.

  As the polyoxyalkylene (C2 to C3) polyol, specifically, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene-polyoxypropylene glycol (random and / or random mixture of propylene oxide and ethylene oxide) Block copolymer).

  In addition, the polyoxyalkylene (2 to 3 carbon atoms) polyol further includes polytrimethylene glycol and the like.

  Examples of the polytrimethylene ether glycol include a glycol obtained by a polycondensation reaction of 1,3-propanediol derived from a plant component.

  Examples of the polytetramethylene ether polyol include a ring-opened polymer (polytetramethylene ether glycol (crystalline)) obtained by cationic polymerization of tetrahydrofuran, an alkyl-substituted tetrahydrofuran, An amorphous (non-crystalline) polytetramethylene ether glycol obtained by copolymerizing an alcohol is exemplified.

  Examples of the polyester polyol include a polycondensate obtained by reacting a monomer polyol and a polybasic acid under known conditions.

  Examples of the monomer polyol include the above-described monomer polyols, and preferably include a dihydric alcohol.

  Examples of polybasic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid Aliphatic dicarboxylic acids (C11-13) such as azelaic acid and sebacic acid, for example, unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, for example, phthalic acid, isophthalic acid, terephthalic acid, toluene Dicarboxylic acids, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, for example, alicyclic dicarboxylic acids such as hexahydrophthalic acid, for example, dimer acid, hydrogenated dimer acid, and other carboxylic acids such as het acid, and their carboxylic acids Acid anhydrides derived from acids such as oxalic anhydride, succinic anhydride, maleic anhydride, Phthalic acid, 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and acid halides derived from these carboxylic acids and the like, for example, oxalic acid dichloride, adipic dichloride, Sebacic acid dichloride and the like.

  These polybasic acids can be used alone or in combination of two or more.

  The polybasic acid preferably includes a saturated aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and an acid anhydride.

  As the polyester polyol, for example, a plant-derived polyester polyol, specifically, the above-mentioned monomer polyol is used as an initiator, and a hydroxyl group-containing vegetable oil fatty acid (for example, castor oil fatty acid containing ricinoleic acid, 12-hydroxystearin Vegetable oil-based polyester polyols obtained by subjecting a hydroxycarboxylic acid such as an acid-containing hydrogenated castor oil fatty acid) to a condensation reaction under known conditions.

  As the polyester polyol, for example, the above-mentioned monomer polyol (preferably, a di- to tri-hydric alcohol) is used as an initiator, for example, lactones such as ε-caprolactone, γ-valerolactone, and L-lactide, for example. And lactone-based polyester polyols such as polycaprolactone polyol and polyvalerolactone polyol obtained by ring-opening polymerization of lactides such as D-lactide and the like. Further, alcohols obtained by copolymerizing the above dihydric alcohols with them. And modified lactone polyols.

  Examples of the polycarbonate polyol include, for example, a ring-opened polymer (crystalline polycarbonate polyol) of ethylene carbonate using the above-mentioned monomer polyol (preferably, the above-mentioned dihydric alcohol) as an initiator, and, for example, those having 4 to 6 carbon atoms. Amorphous copolymer of dihydric alcohol (1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, etc.) and a ring-opening polymer Polycarbonate polyols and the like. Also, a plant-derived polycarbonate polyol derived from a plant-derived material such as isosorbide may be used. The term “amorphous” indicates that the material is liquid at normal temperature (25 ° C.). The term “crystalline” means that the compound is solid at normal temperature (25 ° C.).

  These polymer polyols can be used alone or in combination of two or more.

  As the polymer polyol, from the viewpoint of improving low-temperature curability and friction fastness, preferably, a polyether polyol and a polyester polyol (preferably, a lactone-based polyester polyol) are used, and more preferably, a polyether polyol is used. And more preferably polytetramethylene ether polyol.

  These polyols can be used alone or in combination of two or more.

  Preferably, the polyol is a polymer polyol.

  The molecular weight of the polyol (the average molecular weight of the polyol when a plurality is used in combination) is, for example, 60 or more, preferably 100 or more, more preferably 120 or more, and still more preferably, from the viewpoint of low-temperature curability and friction fastness. Is 150 or more, more preferably 200 or more, particularly preferably 300 or more, for example, 5000 or less, preferably 3000 or less, more preferably 2000 or less, further preferably 1500 or less, particularly preferably, 1000 or less.

  When the molecular weight of the polyol is within the above range, excellent low-temperature curability and friction fastness can be obtained.

  The molecular weight of the monomer polyol can be calculated from the molecular skeleton and the number of atoms. Further, the molecular weight of the polymer polyol is determined as a number average molecular weight as a standard polystyrene equivalent molecular weight determined by gel permeation chromatography. Then, the molecular weight of the polyol is calculated as an average value of the molecular weight of each component.

  The average number of functional groups of the polyol is, for example, 2 or more, for example, 8 or less, preferably 6 or less, more preferably 4 or less, further preferably 3 or less, from the viewpoint of low-temperature curability and friction fastness. The following is especially preferred.

  The monol is an organic compound having one hydroxyl group in a molecule, and includes a monomer monol and a polymer monol.

  Monomer monool is an organic monomer having one hydroxyl group in the molecule, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, s-butanol, t-butanol, hexanol, cyclohexanol, heptanol Octanol, 2-ethylhexanol, nonyl alcohol, isononyl alcohol, decanol (carbon number 10), lauryl alcohol (carbon number 12), cetyl alcohol (carbon number 14), stearyl alcohol (carbon number 18), oleyl alcohol (carbon (Equation 18), aliphatic monools such as eicosanol (carbon number 20), for example, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol monomethyl ether (also known as methyl cellosolve) Ether monools such as diethylene glycol monoethyl ether (also known as ethyl carbitol), for example, phenol and its derivatives, benzyl alcohol and its derivatives, phenethyl alcohol and derivatives thereof, and aromatic alcohols such as naphthol and derivatives thereof.

  These monomer monols can be used alone or in combination of two or more.

  As the monomer monool, preferably, an aliphatic monool is used, more preferably, an aliphatic monool having 2 to 6 carbon atoms is used, and still more preferably, isobutanol is used.

The polymer monol is an organic polymer having one hydroxyl group in a molecule, and includes, for example, a sealed body in which a terminal of a polymer polyol is sealed with an alkyl group or the like except for one terminal. .

  More specifically, for example, a sealed body in which one end of a bifunctional polymer polyol (polymer diol) is sealed with an alkyl group or the like (hereinafter, may be referred to as a single-ended polymer diol). And the like.

  Examples of the polymer diol having one end-capping include polyether diol having one end-capping, polyester diol having one terminal-capping, polycarbonate diol having one terminal-capping, polyurethane diol having one terminal-capping, epoxydiol having one terminal-capping, and one terminal. Examples thereof include a sealed vegetable oil diol, a polyolefin diol with a single end, an acrylic diol with a single end, a diol modified with a vinyl monomer with a single end, and preferably a polyether diol with a single end.

  More preferably, the polyether diol having a single terminal is polyoxyethylene glycol having a single terminal and polyoxyethylene-polyoxypropylene glycol having one terminal.

  One-end-blocked polyoxyethylene glycol is a polyethylene glycol monoalkyl ether in which one terminal hydroxyl group of polyoxyethylene glycol is sealed with an alkyl group (that is, the hydroxyl group is substituted with an oxyalkylene group).

  The one-end-blocked polyoxyethylene-polyoxypropylene glycol is not particularly limited, and can be obtained by a known method.

  In the polyethylene glycol monoalkyl ether, the alkyl group has 1 or more carbon atoms, for example, 20 or less, preferably 8 or less, more preferably 6 or less, further preferably 4 or less, particularly preferably 2 or less. It is. That is, examples of the alkyl group for sealing one end include a methyl group and an ethyl group.

  Specific examples of such a polyethylene glycol monoalkyl ether include polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether.

  One-end-blocked polyoxyethylene-polyoxypropylene glycol is a polyoxyethylene-polyoxypropylene glycol in which one terminal hydroxyl group of polyoxyethylene-polyoxypropylene glycol is sealed with an alkyl group (that is, the hydroxyl group is substituted with an oxyalkylene group). Oxypropylene glycol monoalkyl ether.

  The one-end-blocked polyoxyethylene-polyoxypropylene glycol is not particularly limited, and can be obtained by a known method. Specifically, for example, ethylene oxide and propylene oxide are added using a monohydric alcohol (monoalkyl ether of dipropylene glycol or the like) in which one terminal hydroxyl group of the above dihydric alcohol is blocked with an alkyl group as an initiator. It can be obtained by reacting.

  In polyoxyethylene-polyoxypropylene glycol monoalkyl ether, the number of carbon atoms of the alkyl group is 1 or more, for example, 20 or less, preferably 8 or less, more preferably 6 or less, further more preferably 4 or less, Particularly preferably, it is 2 or less. That is, as the alkyl group for sealing one end, preferably, a methyl group or an ethyl group is used.

  Specific examples of such polyoxyethylene-polyoxypropylene glycol monoalkyl ether include polyoxyethylene-polyoxypropylene glycol monomethyl ether, polyoxyethylene-polyoxypropylene glycol monoethyl ether, and the like.

  In the polyoxyethylene-polyoxypropylene glycol monoalkyl ether, the ratio of the oxyethylene group to the total mass of the oxyethylene group and the oxypropylene group is, for example, 1% by mass or more from the viewpoint of low-temperature curability and friction fastness. Preferably, it is 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, for example, 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less. %, More preferably 70% by mass or less.

  These polymer monols can be used alone or in combination of two or more.

  As the polymer monol, preferably, from the viewpoint of low-temperature curability and friction fastness, one end-blocked polyoxyethylene-polyoxypropylene glycol is used.

  These monols can be used alone or in combination of two or more.

  As the monol, preferably, a polymer monol is used alone, or a polymer monol and a monomer monol are used in combination. More preferably, a polymer monol is used alone.

  When the polymer monol and the monomer monol are used in combination, the combination ratio is, from the viewpoint of low-temperature curability and friction fastness, the amount of the polymer monool is, for example, 50 moles based on the total moles thereof. %, Preferably 70 mol% or more, for example, 90 mol% or less, preferably 80 mol% or less. Further, the content of the monomer monool is, for example, 10 mol% or more, preferably 20 mol% or more, and for example, 50 mol% or less, preferably 30 mol% or less.

  The molecular weight of the monol (when a plurality is used in combination, the average molecular weight of the monol) is, for example, 50 or more, preferably 100 or more, more preferably 200 or more from the viewpoint of low-temperature curability and friction fastness. More preferably, it is 400 or more, and from the viewpoint of low-temperature curability and friction fastness, for example, it is 5000 or less, preferably 3000 or less, more preferably 2000 or less, and further preferably 1000 or less.

  If the molecular weight of the monol is within the above range, excellent low-temperature curability and friction fastness can be obtained.

  The molecular weight of the monomer monol can be calculated from the molecular skeleton and the number of atoms. Further, the molecular weight of the polymer monol is determined as a number average molecular weight and as a polystyrene equivalent molecular weight by gel permeation chromatography. Then, the molecular weight of the monol is calculated as an average value of the molecular weights of the components.

  In alcohols, the combination ratio of the polyol and the monol is set based on the molar ratio between the number of hydroxyl groups derived from the polyol and the number of hydroxyl groups derived from the monol.

  Specifically, from the viewpoint of low-temperature curability and friction fastness, the molar ratio of the number of hydroxyl groups derived from the polyol to the number of hydroxyl groups derived from the monool (hydroxyl group derived from polyol / hydroxyl group derived from monol) is, for example, 0.1. Or more, preferably 0.5 or more, more preferably 0.8 or more, for example, less than 2.0, preferably 1.8 or less, more preferably 1.5 or less, and still more preferably 1 or less. .2 or less.

  That is, a polycarbodiimide composition containing a carbodiimide modified product is prepared by first reacting a linear aliphatic diisocyanate as a raw material component with the above-mentioned alcohols (monool and polyol) under predetermined conditions, and obtaining an isocyanate group as a reaction product. After obtaining the terminal prepolymer, it can be further obtained by subjecting the isocyanate group-terminated prepolymer to a carbodiimidation reaction.

  In such a case, if the combination ratio of the polyol and the monol is within the above range, a prepolymer having a moderately high molecular weight is obtained by a reaction (described later) between the linear aliphatic diisocyanate and the alcohol, The prepolymer is carbodiimidated. Therefore, compared with the case where the modified carbodiimide has a relatively high molecular weight and a relatively low molecular weight, excellent low-temperature curability and friction fastness can be obtained.

  Hereinafter, the method for producing the polycarbodiimide composition will be described in detail.

  In this method, first, the above-mentioned linear aliphatic diisocyanate and the above-mentioned alcohols are urethanized (urethane-forming step).

  In the urethanization step, the reaction ratio between the linear aliphatic diisocyanate and the alcohol is determined by the equivalent ratio of the isocyanate group of the linear aliphatic diisocyanate to the hydroxyl group of the alcohol (NCO / OH), which is the carbodiimide equivalent of the polycarbodiimide composition. (G / mol) is set according to the type (molecular weight, etc.) of the linear aliphatic diisocyanate and the alcohol such that the range is as described below.

  More specifically, depending on the type of the linear aliphatic diisocyanate and the alcohol, the reaction ratio between the linear aliphatic diisocyanate and the alcohol is based on the isocyanate group of the linear aliphatic diisocyanate with respect to the hydroxyl group of the alcohol. The equivalent ratio (NCO / OH) is, for example, more than 2, preferably 3 or more, more preferably 4 or more, further preferably 5 or more, for example, 16 or less, preferably 10 or less, Preferably, it is less than 8, more preferably 6 or less. That is, in the urethanization step, the reaction is preferably performed at a ratio at which the isocyanate group is excessive relative to the hydroxyl group.

  If the reaction ratio between the linear aliphatic diisocyanate and the alcohol is within the above range, excellent low-temperature curability and friction fastness can be obtained.

  In this reaction, if necessary, a known urethanization catalyst such as an amine or an organic metal compound may be added.

  As the amines, for example, tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, and the like, for example, quaternary ammonium salts such as tetraethylhydroxylammonium, for example, imidazole, And imidazoles such as 2-ethyl-4-methylimidazole.

  Examples of the organometallic compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate (dilauric acid). Organic tin-based compounds such as dibutyltin (IV)), dibutyltin dinedecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, and dibutyltin dichloride; for example, organic lead compounds such as lead octanoate and lead naphthenate; Organic nickel compounds such as nickel naphthenate; for example, organic cobalt compounds such as cobalt naphthenate; organic copper compounds such as copper octenoate; and organic bismuth compounds such as bismuth octylate and bismuth neodecanoate. It is.

  Further, examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

  These urethanization catalysts can be used alone or in combination of two or more.

  The mixing ratio of the urethanization catalyst is not particularly limited, and is appropriately set according to the purpose and use.

  The reaction conditions in the urethanization step are such that the carbodiimide equivalent (g / mol) of the polycarbodiimide composition falls within the range described below, and the type of the linear aliphatic diisocyanate and the alcohol and the above-mentioned equivalent ratio (NCO / OH) or the like.

  More specifically, the reaction conditions in the urethanization step are, for example, a reaction temperature of, for example, 30 ° C. or higher, preferably 60 ° C. or higher under normal pressure and an inert gas (eg, nitrogen gas) atmosphere. For example, it is 150 ° C. or lower, preferably 120 ° C. or lower. The reaction time is, for example, 1 hour or more, preferably 3 hours or more, and for example, 50 hours or less, preferably 40 hours or less.

  As a result, a prepolymer can be obtained as a reaction product of a linear aliphatic diisocyanate and an alcohol. In addition, the prepolymer has an isocyanate group at the molecular terminal (that is, isocyanate group-terminated prepolymer).

  Next, in this method, the reaction solution containing the reaction product in the urethane-forming step is heated in the presence of a carbodiimidation catalyst to cause a carbodiimidization reaction (carbodiimidization step).

  The carbodiimidization catalyst is not particularly limited, and examples thereof include a trialkyl phosphate ester compound, a phosphorene oxide compound, a phosphorene sulfide compound, a phosphine oxide compound, and a phosphine compound.

  Examples of the trialkyl phosphate include a trialkyl phosphate ester-based compound having 3 to 24 carbon atoms such as trimethyl phosphate, triethyl phosphate, and trioctyl phosphate.

  Examples of the phospholene oxide-based compound include 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO), 1-ethyl-3-methyl-2-phospholene-1-oxide (EMPO), -Butyl-3-methyl-2-phospholene-1-oxide, 1-benzyl-3-methyl-2-phospholene-1-oxide, 1,3-dimethyl-2-phospholene-1-oxide, 1-phenyl-2 -Phosphorene oxide having 4 to 18 carbon atoms, such as phosphorene-1-oxide, 1-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide and double bond isomers thereof And the like.

  Examples of the phosphorene sulfide-based compound include a phosphorene sulfide-based compound having 4 to 18 carbon atoms such as 1-phenyl-2-phospholene-1-sulfide.

  Examples of the phosphine oxide compound include a phosphine oxide compound having 3 to 21 carbon atoms such as triphenylphosphine oxide and tolylphosphine oxide.

  Examples of the phosphine-based compound include a phosphine-based compound having 3 to 30 carbon atoms, such as bis (oxadiphenylphosphino) ethane.

  These carbodiimidization catalysts can be used alone or in combination of two or more.

  As the carbodiimidization catalyst, preferably, a phosphorene oxide-based compound is used, and more preferably, 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene- is used. 1-oxide.

  By using the above carbodiimidization catalyst, the activity of carbodiimidization can be improved, the reaction temperature can be lowered, and a side reaction such as uretonimine formation can be suppressed to obtain a polycarbodiimide composition in good yield. And the content of the carbodiimide group can be improved.

  As the carbodiimidization catalyst, 3-methyl-1-phenyl-2-phospholene-1-oxide is particularly preferable from the viewpoint of obtaining excellent low-temperature curability and friction fastness.

  The compounding ratio of the carbodiimidization catalyst is, for example, 0.01 part by mass or more, preferably 0.05 part by mass, based on 100 parts by mass of the linear aliphatic diisocyanate (the linear aliphatic diisocyanate used in the urethane-forming step). Or less, for example, 20 parts by mass or less, preferably 10 parts by mass or less.

  The reaction conditions in the carbodiimidation step are set so that the content ratio (carbodiimide equivalent) of the carbodiimide group in the obtained polycarbodiimide composition falls within a specific range described later. More specifically, from the viewpoint of promoting the carbodiimidation reaction and reducing uretonimine, the reaction temperature is, for example, 125 ° C. or higher, preferably at normal pressure and in an inert gas (such as nitrogen gas) atmosphere, 130 ° C. or higher, more preferably 135 ° C. or higher, for example, 180 ° C. or lower, preferably 170 ° C. or lower, more preferably 160 ° C. or lower. The reaction time is, for example, 1 hour or more, preferably 3 hours or more, and for example, 50 hours or less, preferably 40 hours or less.

  By reacting under such conditions, the reaction product (isocyanate group-terminated prepolymer) obtained in the urethane-forming step undergoes decarboxylation condensation via the isocyanate group, and a carbodiimide group can be efficiently generated.

  More specifically, when the reaction temperature is equal to or higher than the lower limit, the carbodiimidization reaction can be advanced while promoting the reaction of decomposing the generated uretonimine into carbodiimide and isocyanate groups. When the temperature is lower than the above lower limit, the thermal decomposition reaction becomes very difficult to occur, the content of uretonimine increases, and the content of carbodiimide groups decreases. In addition, the molecular weight may increase due to an increase in uretonimine, and the reaction solution may be solidified. On the other hand, when the reaction temperature is equal to or lower than the upper limit, the polymerization loss can be reduced. When the temperature exceeds the upper limit temperature, polymerization reactions other than carbodiimidization and uretonimine are promoted, and not only the content of carbodiimide groups is reduced, but also the reaction liquid is easily solidified due to an increase in molecular weight.

  In the carbodiimidization step, the reaction liquid is preferably refluxed in the presence of an organic solvent, from the viewpoint of smoothly causing a carbodiimidization reaction and promoting decarboxylation condensation. That is, the carbodiimidization reaction is performed under reflux.

  As the organic solvent, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, for example, nitriles such as acetonitrile, methyl acetate, ethyl acetate, butyl acetate, butyl acetate, isobutyl acetate, alkyl esters such as amyl acetate, for example , N-hexane, n-heptane, aliphatic hydrocarbons such as octane, for example, cyclohexane, alicyclic hydrocarbons such as methylcyclohexane, for example, toluene, xylene, aromatic hydrocarbons such as ethylbenzene, for example, Methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol Glycol ether esters such as coal monomethyl ether acetate (PMA), 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, for example, diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diethylene glycol Ethers such as dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, ethylene glycol diethyl ether 1,2-diethoxyethane, for example, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide , Methylene iodide, dichloroethane, and other halogenated aliphatic hydrocarbons such as N-methylpyrrolidone, dimethylformamide, N N'- dimethylacetamide, dimethyl sulfoxide, such as a polar aprotic such as hexamethylphosphoric phosphonyl amides. These organic solvents can be used alone or in combination of two or more.

  As the organic solvent, preferably, an organic solvent whose temperature at reflux is within the above-mentioned reaction temperature range is exemplified.

  Specific examples of such an organic solvent include xylene, ethylene glycol methyl ether acetate, and propylene glycol methyl ether acetate.

  The blending ratio of the organic solvent is not particularly limited, but from the viewpoint of obtaining excellent low-temperature curability and friction fastness, based on 100 parts by mass of the linear aliphatic diisocyanate (linear aliphatic diisocyanate used in the urethane-forming step). Thus, for example, it is 50 parts by mass or more, preferably 100 parts by mass or more, and for example, 2000 parts by mass or less, preferably 500 parts by mass or less.

  By refluxing the reaction solution in the presence of the organic solvent, the carbodiimidization reaction can be smoothly performed while promoting the decomposition reaction of uretonimine, and the carbon dioxide gas generated due to the carbodiimidization of the isocyanate group is eliminated. Therefore, carbodiimidization can be promoted.

  By such a method, a modified carbodiimide containing a urethane group and a carbodiimide group, and optionally containing a uretonimine group can be obtained.

  More specifically, first, in the urethane-forming step, a urethane group derived from the isocyanate group of the linear aliphatic diisocyanate is generated.

  Next, when the reaction product (isocyanate group-terminated prepolymer) obtained in the urethanization step is heated in the carbodiimidization step, a carbodiimide group derived from the isocyanate group at the molecular end is formed, and in some cases, the carbodiimide group is formed. A part of the carbodiimide group reacts with an isocyanate group at a molecular terminal to generate a uretonimine group. The uretonimine group is thermally decomposed by continuing heating in the carbodiimidization step, the carbodiimide group and the molecular end isocyanate group are regenerated, and further, a carbodiimide group derived from the molecular end isocyanate group is generated. .

  In this way, the isocyanate group of the linear aliphatic diisocyanate is converted into a urethane group and a carbodiimide group (and optionally a uretonimine group).

  As a result, a modified carbodiimide containing a urethane group and a carbodiimide group, and optionally containing a uretonimine group is obtained.

  Thus, a polycarbodiimide composition containing a modified carbodiimide as a main component is obtained. In addition, the polycarbodiimide composition may contain an unreacted straight-chain aliphatic diisocyanate as an accessory component. The content ratio of the linear aliphatic diisocyanate is appropriately set within a range that does not impair the excellent effects of the present invention.

  In this method, if necessary, the polycarbodiimide composition obtained in the carbodiimidization step and an alcohol can be further reacted. In the following, the urethane-forming step before the carbodiimidation step may be referred to as a first urethane-forming step, and the urethane-forming step after the carbodiimidation step may be referred to as a second urethane-forming step.

  Specifically, when the polycarbodiimide composition obtained in the carbodiimidization step further has an isocyanate group at a molecular terminal, the polycarbodiimide composition is reacted with an alcohol to form an isocyanate at the molecular terminal. The group can be urethanized.

  When the second urethanization step is performed, the amount of by-products derived from alcohols increases, the molecular weight sharply increases, the fluidity decreases, and the workability decreases. In some cases, the dispersibility of the material may decrease. Therefore, preferably, only the first urethane-forming step and the carbodiimidization step are performed without performing the second urethane-forming step.

  The method for producing the polycarbodiimide composition is not limited to the above. For example, a straight-chain aliphatic diisocyanate, a carbodiimidization catalyst, and an alcohol may be combined and heated.

  Further, if necessary, from the polycarbodiimide composition, for example, unreacted linear aliphatic diisocyanate, unreacted alcohols, low molecular weight compounds (by-products), organic solvents, carbodiimidization catalysts, urethanization catalysts, etc. Can be removed by a known method such as distillation, extraction, or filtration.

  If necessary, the polycarbodiimide composition may further contain a known additive such as a storage stabilizer (eg, o-toluenesulfonamide, p-toluenesulfonamide), a plasticizer, an antiblocking agent, and a heat-resistant stabilizer. Agents, light stabilizers, antioxidants, release agents, catalysts, pigments, surface conditioners, dispersants, dyes, lubricants, fillers, hydrolysis inhibitors, and the like can be added at appropriate timing. In addition, the addition ratio of the additive is not particularly limited, and is appropriately set according to the purpose and use.

  The polycarbodiimide compositions can be used alone or in combination of two or more.

  The carbodiimide equivalent (g / mol) of the polycarbodiimide composition thus obtained is, for example, 300 or more, preferably 350 or more, more preferably 400 or more, still more preferably 410 or more, and particularly preferably 430 or more. The above is 550 or less, preferably 530 or less, more preferably 500 or less, further preferably 480 or less, and particularly preferably 460 or less.

The carbodiimide equivalent (g / mol) is measured by ¹³ C-NMR according to the examples described later.

That is, the carbodiimide equivalent (g / mol) can be calculated from the charging ratio, but an actually measured value by ¹³ C-NMR is employed.

  Further, since such a polycarbodiimide composition uses alcohols containing a polyol and a monool at a predetermined ratio, the polycarbodiimide composition has a higher molecular weight than a polycarbodiimide composition using only a monool, and a low-molecular-weight substance is used. Has been reduced.

Specifically, in the chromatogram when the polycarbodiimide composition was measured by gel permeation chromatography, the area ratio of the peak area of the polystyrene-equivalent molecular weight of 500 or less to the total peak area was:
From the viewpoint of obtaining excellent friction fastness, for example, 10.0% or less, preferably 8.0% or less, more preferably 7.0% or less, still more preferably 6.5% or less, still more preferably , 6.0% or less, more preferably 5.0% or less, particularly preferably 4.5% or less.

Further, in the chromatogram when the polycarbodiimide composition was measured by gel permeation chromatography, the area ratio of the peak area of the polystyrene-equivalent molecular weight of 1000 or less to the total peak area was:
From the viewpoint of obtaining excellent friction fastness, for example, 15.0% or less, preferably 12.0% or less, more preferably 10.0% or less, still more preferably 9.0% or less, and still more preferably , 8.0% or less, particularly preferably 7.0% or less.

  The area ratio was determined by measuring the molecular weight distribution of an isocyanurate derivative of pentamethylene diisocyanate by a gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID) in accordance with Examples described later. It can be calculated as the area ratio in the obtained chromatogram (chart). The area ratio of the peak area having a molecular weight of 500 or less and the area ratio of the peak area having a molecular weight of 1000 or less are based on the calibration curve of standard polystyrene.

  When the area ratio of the peak area having a molecular weight of 500 or less is within the above range and the area ratio of the peak area having a molecular weight of 1000 or less is within the above range, the low-temperature curability and the friction fastness can be improved.

  The carbodiimide crosslinking agent for fiber treatment is not particularly limited as long as it contains the polycarbodiimide composition. For example, an aqueous dispersion in which the polycarbodiimide composition is dispersed in water (hereinafter, referred to as an aqueous dispersion composition) or the like. And a solution in which the polycarbodiimide composition is dissolved in an organic solvent (hereinafter, referred to as a solution composition).

  The aqueous dispersion composition contains the polycarbodiimide composition and water.

  The method for dispersing the polycarbodiimide composition in water is not particularly limited, and examples thereof include a method of adding water to the polycarbodiimide composition and stirring, and a method of adding the polycarbodiimide composition to water and stirring. . Preferably, water is added to the polycarbodiimide composition.

  The ratio between the polycarbodiimide composition and water is not particularly limited, but the concentration of the polycarbodiimide composition (resin component) in the aqueous dispersion composition (that is, the solid content concentration) is, for example, 5% by mass or more, preferably It is 10% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less.

  When the curing agent is an aqueous dispersion composition, compatibility with an aqueous resin (base agent) can be improved, and excellent low-temperature curability and friction fastness can be obtained.

  The solution composition contains a polycarbodiimide composition and an organic solvent.

  Examples of the organic solvent include the above-mentioned organic solvents, preferably, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene.

  Further, the solvent used in the carbodiimidization step may be used as the organic solvent of the solution composition. For example, the solvent used after the carbodiimidation step can be used as it is as the organic solvent of the solution composition without being distilled off.

  The method of dissolving the polycarbodiimide composition in the organic solvent is not particularly limited, and a method of adding an organic solvent to the polycarbodiimide composition and stirring, or a method of adding the polycarbodiimide composition to the organic solvent and stirring Is mentioned. Preferably, an organic solvent is added to the polycarbodiimide composition.

  The ratio between the polycarbodiimide composition and the organic solvent is not particularly limited, but the concentration of the polycarbodiimide composition (resin component) in the solution composition (that is, the solid content concentration) is, for example, 5% by mass or more, preferably It is 10% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less.

  When the curing agent is a solution composition, compatibility with the oil-based resin (base agent) can be improved, and excellent low-temperature curability and friction fastness can be obtained.

  As the carbodiimide crosslinking agent for fiber treatment, an aqueous dispersion of a polycarbodiimide composition is preferably used.

  In the above-mentioned carbodiimide crosslinking agent for fiber treatment, a prepolymer is obtained by a reaction between a linear aliphatic diisocyanate and an alcohol containing a polyol, and the prepolymer is carbodiimidated, and a modified carbodiimide having a relatively high molecular weight is obtained. Is obtained. As a result, by using the carbodiimide crosslinking agent for fiber treatment, it is possible to improve the fastness to friction when printing at a relatively low temperature (120 ° C. or lower).

  More specifically, the carbodiimide crosslinking agent for fiber treatment is suitably used as a printing ink raw material for textile printing.

  The printing ink raw material includes the above-described crosslinking agent as a polyisocyanate component and a main agent having a carboxyl group.

  Examples of the main agent having a carboxyl group include an aqueous resin having a carboxyl group and an oil-based resin having a carboxyl group.

  Examples of the aqueous resin having a carboxyl group include, for example, a hydrophilic polymer having a carboxyl group, and specifically, a hydrophilic polyester resin having a carboxyl group, a hydrophilic polyamide resin having a carboxyl group, and having a carboxyl group. Hydrophilic polyurethane resin (hydrophilic polyurethane polyol), hydrophilic acrylic resin having carboxyl group (hydrophilic acrylic polyol), hydrophilic polyolefin having carboxyl group (for example, polypropylene, polyethylene, polypropylene-polyethylene (random block)) And a polyolefin resin having a repeating unit having 4 or more carbon atoms. These aqueous resins having a carboxyl group can be used alone or in combination of two or more.

  Preferred examples of the aqueous resin having a carboxyl group include a hydrophilic polyurethane resin having a carboxyl group (hydrophilic polyurethane polyol) and a hydrophilic acrylic resin having a carboxyl group (hydrophilic acrylic polyol).

  Examples of the oil-based resin having a carboxyl group include, for example, a hydrophobic polymer having a carboxyl group, specifically, a hydrophobic polyester resin having a carboxyl group, a hydrophobic polyamide resin having a carboxyl group, and a carboxyl group. Having a hydrophobic polyurethane resin (hydrophobic polyurethane polyol), a hydrophobic acrylic resin having a carboxyl group (hydrophobic acrylic polyol), and a hydrophobic polyolefin having a carboxyl group (for example, polypropylene, polyethylene, polypropylene-polyethylene (random block)) Polymers, and other polyolefin resins having 4 or more carbon atoms in the repeating unit). These oil-based resins having a carboxyl group can be used alone or in combination of two or more.

  Preferred examples of the oil-based resin having a carboxyl group include a hydrophobic polyurethane resin having a carboxyl group (hydrophobic polyurethane polyol) and a hydrophobic acrylic resin having a carboxyl group (hydrophobic acrylic polyol).

  These can be used alone or in combination of two or more.

  Preferably, the main agent and the cross-linking agent include a combination in which the main agent is an aqueous resin and the cross-linking agent is an aqueous dispersion composition. Also preferably, a combination in which the main agent is an oil-based resin and the cross-linking agent is a solution composition is used.

  From the viewpoint of reducing the organic solvent and protecting the global environment, preferably, a combination of an aqueous base agent and an aqueous dispersion composition is used.

  Then, a printing ink is prepared from such a two-component printing ink raw material (base agent and crosslinking agent).

  Such a printing ink raw material is not particularly limited as long as it contains the above-described main agent and the above-described crosslinking agent, and is a two-pack type in which the main agent and the crosslinking agent are separately prepared and mixed at the time of use. Or a one-pack type in which a main agent and a crosslinking agent are mixed in advance.

  As a printing ink raw material, preferably, a two-pack type printing ink raw material is used.

  The content ratio of the main agent and the crosslinking agent is, in terms of solid content, the main agent is, for example, 10 parts by mass or more, preferably 30 parts by mass or more based on 100 parts by mass of the total amount thereof, for example, 99.5 parts by mass. Parts by weight, preferably 95.0 parts by weight or less. The amount of the crosslinking agent is, for example, 0.5 parts by mass or more, preferably 5 parts by mass or more, and for example, 90 parts by mass or less, preferably 70 parts by mass or less.

  Further, the molar ratio of the carbodiimide group in the crosslinking agent to the carboxyl group in the main agent is, for example, 0.1 or more, preferably 0.2 or more, more preferably 0.5 or more. 5 or less, preferably 2.0 or less, more preferably 1.5 or less.

  Further, a pigment is preferably blended with either or both of the crosslinking agent and the main agent. The pigment is not particularly limited, and examples thereof include a blue pigment, a white pigment, and a black pigment.

  The mixing ratio of the pigment is, for example, 1% by mass or more, preferably 10% by mass or more, for example, 40% by mass or less, and preferably 30% by mass or less, based on the total amount of the crosslinking agent, the main agent, and the pigment.

  In addition, one or both of the cross-linking agent and the main agent may include, as necessary, for example, an epoxy resin, a catalyst (such as a urethane-forming catalyst), a coating improver, a leveling agent, a viscosity modifier, a defoaming agent, Additives such as stabilizers such as antioxidants and ultraviolet absorbers, plasticizers, surfactants, surface conditioners, dispersants, fillers, organic or inorganic fine particles, fungicides, silane coupling agents, etc. Is also good. The amounts of these additives are appropriately determined depending on the purpose and use.

  Further, as the main agent, the above-mentioned water-based resin having a carboxyl group and / or the above-mentioned oil-based resin having a carboxyl group, and other resins (for example, a hydroxyl-containing polyurethane resin, a hydroxyl-containing acrylic resin, a hydroxyl-containing polyester resin, etc. ) Can also be used in combination.

  Further, as the crosslinking agent, the above-mentioned polycarbodiimide composition can be used in combination with another crosslinking agent (for example, a polyisocyanate-based resin (such as a block polyisocyanate), an epoxy-based resin, or a melamine resin).

  The printing ink is printed (printed) on an object to be printed by a known printing apparatus (for example, an ink jet apparatus), and then heat-treated and cured as necessary.

  As an object to be printed, for example, a fiber is cited, and more specifically, a cloth, leather and the like are cited.

  The fibers of the fabric are not particularly limited, and include, for example, natural fibers (eg, silk, cotton, hemp, etc.) and synthetic fibers (eg, nylon, polyester, rayon, etc.). The form of the fabric is not particularly limited, and examples thereof include a woven fabric, a knitted fabric, and a nonwoven fabric. The leather is not particularly limited, and examples thereof include natural leather and artificial leather.

  The heating temperature is relatively low, more specifically, 120 ° C. or lower, preferably 100 ° C. or lower, more preferably 80 ° C. or lower. Usually, it is 5 ° C. or higher, more preferably 20 ° C. or higher.

  Thereby, a cured ink (cured coating film, polyurethane resin) is formed. Since the obtained cured ink is formed from the above-described ink for textile printing, it has excellent low-temperature curability and friction fastness.

  Next, the present invention will be described based on Production Examples, Examples and Comparative Examples, but the present invention is not limited by the following Examples. Note that “parts” and “%” are based on mass unless otherwise specified. In addition, specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are the mixing ratios (corresponding to those described in the above “Embodiment of the Invention”). Substitute the upper limit value (value defined as “less than” or “less than”) or the lower limit value (value defined as “over” or “exceeding”) such as content ratio, physical property value, parameter, etc. be able to.

<IR spectrum>
Completion of the carbodiimidization reaction in the method for producing a polycarbodiimide composition was confirmed by measuring an IR spectrum using the following apparatus and conditions.

IR measuring device: Frontier FT-IR manufactured by Perkin Elmer
Measurement method: ATR (reflection method)
Wave number range: 4000-400 cm ^-1
Resolution 4cm ^-1
<Carbodiimide equivalent (g / mol) of polycarbodiimide composition>
The carbodiimide equivalent of the polycarbodiimide composition was determined from ¹³ C-NMR measurement. Further, as a reference value, a calculated value of a carbodiimide equivalent from the charged amount was obtained.

That is, ¹³ C-NMR was measured using the following apparatus and conditions, and the content ratio of the uretonimine group to the total of 1 mol of the carbodiimide group, uretonimine group, allophanate group, and urethane group was calculated by the following equation. Incidentally, as a reference for the chemical shift ppm, using tetramethylsilane CDCL ₃ solvent (0 ppm).
Equipment; ECA-500 type (manufactured by JEOL)
Conditions: Measurement frequency: 125 MHz, solvent: CDCL ₃ , solute concentration: 50% by mass
Measurement temperature: room temperature, 8500 scans Repetition time: 3.0 seconds, pulse width: 30 ° (3.70 μs)
Assigned peak of carbon of carbodiimide group (N = C = N group in carbodiimide group): 139 ppm
Assigned peak of carbon of ureton imine group (C = O group, C = N group in ureton imine group): 159 ppm, 145 ppm
Assigned peak of carbon of allophanate group (C = O group in allophanate group): 154 ppm
Assigned peak of carbon of urethane group (C = O group in urethane group)
: 156 ppm
(Carbodiimide equivalent) = {(weight of solid content charged) − (molar ratio of carbon dioxide generated to urethane group) × (total number of moles of alcohol charged) × 44.01} / {(molar ratio of carbodiimide group to urethane group) ) X (total number of moles of alcohol charged)
The molar ratio of carbon dioxide generated to urethane groups and the molar ratio of carbodiimide groups to urethane groups are calculated as follows.

(Molar ratio of carbon dioxide generated to urethane groups) = {(integrated value of carbodiimide group) + (integrated value of uretonimine group)} / {(integrated value of urethane group) + (integrated value of allophanate group)}
(Molar ratio of carbodiimide group to urethane group) = (integrated value of carbodiimide group) / {(integrated value of urethane group) + (integrated value of allophanate group)}
<Area ratio>
According to a gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID), a ratio of a peak area having a polystyrene-equivalent molecular weight of 500 or less to a total peak area, based on a chromatogram obtained under the following GPC measurement conditions, The ratio of the peak area having a polystyrene equivalent molecular weight of 1,000 or less to the total peak area was determined.

  FIG. 1 shows a GPC chromatogram of the polycarbodiimide composition obtained in Example 1 described later. Further, in the figure, peak number / retention time / molecular weight of peak top are also shown.

Equipment: HLC-8320GPC (Tosoh Corporation)
Column; 3 LF-804 (trade name, manufactured by Shodex) connected in series Column temperature: 40 ° C
Eluent; tetrahydrofuran Flow rate: 1.0 mL / min
Detection method; Differential refractive index Standard substance: Standard polystyrene Production Example 1 (production of pentane diisocyanate)
By the same operation as in Example 1 in the specification of International Publication Pamphlet WO2012 / 121291, 99.9% by mass of 1,5-pentanediisocyanate (hereinafter sometimes abbreviated as PDI) was obtained.

Production Example 2 (Production of polyoxyethylene-polyoxypropylene monomethyl ether)
Using dipropylene glycol monomethyl ether as an initiator and potassium hydroxide (KOH) as a catalyst, the mass of ethylene oxide and propylene oxide in a polyol at a temperature of 110 ° C. and a maximum reaction pressure of 0.4 MPa gauge (G). These alkylene oxides (ethylene oxide and propylene oxide) were subjected to random addition polymerization until the hydroxyl value (OHV) became 102 mgKOH / g so that the ratio became 50:50, thereby preparing a crude polyol.

  Then, under a nitrogen atmosphere, ion-exchanged water and 1.05 equivalents of phosphoric acid (in the form of an aqueous solution of 75.2% by weight) relative to KOH were added to the crude polyol heated to 80 ° C. For 2 hours.

  Next, the dehydration under reduced pressure was started while the temperature was raised, and the adsorbent was added when the pressure was 40 kPa. Finally, heating and decompression treatment were performed at 105 ° C. and 1.33 kPa or less for 3 hours.

  Thereafter, the mixture was filtered to obtain polyoxyethylene-polyoxypropylene monomethyl ether.

  In the polyoxyethylene-polyoxypropylene monomethyl ether, the ratio of oxyethylene groups to the total amount of oxyethylene groups and oxypropylene groups (hereinafter referred to as EO ratio) was 50% by mass. The number average molecular weight measured by gel permeation chromatography was 550.

  This polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio: 50% by mass, molecular weight: 550) was defined as monool A.

Example 1
Production of Polycarbodiimide Composition The pentamethylene diisocyanate (PDI) obtained in Production Example 1 was added to a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube at room temperature at 100.0%. Parts by mass, 16.2 parts by mass of PTG-250 (polytetramethylene ether glycol, molecular weight 250), monool A (polyoxyethylene-polyoxypropylene monomethyl ether obtained in Production Example 2 (EO ratio 50% by mass, 71.4 parts by weight of molecular weight 550)) were charged. While introducing nitrogen, the mixture was heated to 80 ° C. under normal pressure and stirred for 4 hours (urethane-forming step).

Subsequently, 758.3 parts by mass of propylene glycol monomethyl ether acetate (PMA) and 2.0 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) were charged, and the mixture was refluxed (150 parts by mass). C.) (carbodiimidization step). Completion of the reaction was confirmed by infrared absorption (IR) spectrum measurement, as the absorption peak near 2260 cm ⁻¹ derived from stretching vibration of the isocyanate group almost disappeared.

After completion of the reaction, the mixture was cooled to 80 ° C., and the PMA was distilled off under reduced pressure until the residual ratio of PMA became 2% or less, to obtain a polycarbodiimide composition. As a result of measuring the obtained polycarbodiimide composition by ¹³ C-NMR, the carbodiimide equivalent was 450 g / mol (calculated value was 317 g / mol).

  A part of the obtained polycarbodiimide composition was taken out, and the E-type viscosity at 25 ° C. was measured. As a result, it was 4000 mPa · s.

Preparation of an aqueous dispersion (aqueous dispersion composition) of a polycarbodiimide composition A polycarbodiimide composition is placed in a flask, distilled water is gradually added so that the resin solid content becomes 40%, and the mixture is stirred to obtain a polycarbodiimide. An aqueous dispersion of the composition was obtained.

Preparation of water-based resin composition An aqueous dispersion of the obtained polycarbodiimide composition was used as a curing agent. Polyurethane dispersion (solid content: 30% by mass, carboxyl group equivalent of 1122 g / mol of solid) was used as the main agent, and mixed so that the equivalent ratio of the carbodiimide group in the curing agent to the carboxyl group in the main agent was 0.5. And a resin composition was prepared.

Example 2
A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 21.2 parts by mass of PTG-250, 62.0 parts by mass of Monol A, and 740.8 parts by mass of PMA were used. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Example 3
A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 9.5 parts by mass of PTG-250, 83.9 parts by mass of Monol A, and 781.9 parts by mass of PMA were used. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Example 4
Example 1 Example 3 was repeated except that 35.1 parts by mass of PTG-650 (polytetramethylene ether glycol, molecular weight 650), 59.5 parts by mass of monool A, and 786.4 parts by mass of PMA were used instead of PTG-250. A polycarbodiimide composition was obtained in the same manner as described above. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Example 5
Example 1 Example 4 was repeated except that 45.9 parts by mass of PTG-850 (polytetramethylene ether glycol, molecular weight 850), 59.5 parts by mass of monool A, and 829.6 parts by mass of PMA were used instead of PTG-250. A polycarbodiimide composition was obtained in the same manner as described above. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Example 6
A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 18.2 parts by mass of PPG-280 (polypropylene glycol, molecular weight 280) and 766.1 parts by mass of PMA were used instead of PTG-250. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Example 7
Monool A (polyoxyethylene-polyoxypropylene monomethyl ether obtained in Production Example 2 (EO ratio: 50% by mass, molecular weight: 550)) and isobutanol were mixed at a molar ratio of 3: 1. This solution was referred to as Monol B.

  Then, a polycarbodiimide composition was obtained in the same manner as in Example 1 except that 55.9 parts by mass of Monol B and 696.6 parts by mass of PMA were used. The analytical values of the obtained polycarbodiimide composition are shown in Table 1 (solution in which polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) and isobutanol were mixed at a molar ratio of 3: 1). In monool B).

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Example 8
Example 1 except that PTG-250 was replaced by 11.3 parts by mass of 1,10-DD (1,10-decanediol), 71.4 parts by mass of monool A, and 738.6 parts by mass of PMA. A polycarbodiimide composition was obtained in the same manner as described above. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Example 9
A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 7.7 parts by mass of 1,6-HD (1,6-hexanediol) and 724.1 parts by mass of PMA were used instead of PTG-250. Was. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Example 10
Example 1 Example 6 was repeated except that 69.5 parts by mass of PTG-1500 (polytetramethylene ether glycol, molecular weight 1500), 51.0 parts by mass of Monol A, and 889.9 parts by mass of PMA were used instead of PTG-250. A polycarbodiimide composition was obtained in the same manner as described above. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Example 11
Polycarbodiimide was produced in the same manner as in Example 1 except that PCL 303 (Placel 303, polycaprolactone triol, molecular weight: 300, manufactured by Daicel) was used in place of PTG-250, and 13.0 parts by mass and 745.3 parts by mass of PMA were used. A composition was obtained. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Example 12
Example 1 except that 100.0 parts by mass of HDI (hexamethylene diisocyanate), 14.9 parts by mass of PTG-250, 65.4 parts by mass of monool A, and 729.1 parts by mass of PMA were used instead of PDI. In the same manner as in 1, a polycarbodiimide composition was obtained. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Example 13
A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 1724.1 parts by mass of PMA and 4.0 parts by mass of MPPO were used. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Comparative Example 1
A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 0.0 parts by mass of PTG-250, 101.9 parts by mass of Monol A, and 815.7 parts by mass of PMA were used. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Comparative Example 2
A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 27.0 parts by mass of PTG-250, 118.9 parts by mass of Monol A, and 991.8 parts by mass of PMA were used. The analytical values of the obtained polycarbodiimide composition are shown in Table 1.

  Further, in the same manner as in Example 1, an aqueous dispersion of the polycarbodiimide composition was prepared, and a resin composition was prepared.

Comparative Example 3
And manufacturing agitator polycarbodiimide composition, a thermometer, a reflux tube, and a four-necked flask equipped with a nitrogen inlet tube, at room temperature, 4,4-200.0 mass dicyclohexylmethane diisocyanate _(H 12 MDI) 2.0 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO). The reaction was carried out at 170 ° C. for 7 hours while introducing nitrogen to obtain a carbodiimide having three carbodiimide groups in one molecule and having isocyanate groups at both ends (carbodiimidization step).

Next, in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube, 100.0 parts by mass of the obtained carbodiimide, 13.6 parts by mass of PTG-250, and UNIOX M550 ( 60.0 parts by mass of polyoxyethylene monomethyl ether, molecular weight 550, manufactured by NOF Corporation was sealed, and reacted at 120 ° C. while introducing nitrogen (urethane-forming step). Completion of the reaction was confirmed by infrared absorption (IR) spectrum measurement, as the absorption peak near 2260 cm ⁻¹ derived from stretching vibration of the isocyanate group almost disappeared.

Preparation of Aqueous Dispersion (Aqueous Dispersion Composition) of Polycarbodiimide Composition The obtained H ₁₂ MDI-derived polycarbodiimide composition is placed in a flask, and while being heated to 80 ° C., the resin solid content becomes 40%. Distilled water was gradually added as described above. After stirring for 5 minutes and then cooling, an aqueous dispersion of the polycarbodiimide composition was obtained.

Preparation of water-based resin composition An aqueous dispersion of the obtained polycarbodiimide composition was used as a curing agent. A hydrophilic polyurethane having a carboxyl group (polyurethane dispersion, solid content 30% by mass, solid carboxyl group equivalent 1122 g / mol) was used as the main agent, and the equivalent ratio of the carbodiimide group in the curing agent to the carboxyl group in the main agent was 0. .5 to prepare a resin composition.

Comparative Example 4
A polycarbodiimide composition was synthesized according to the method described in Synthesis Example 5 of JP-A-2018-104605, and an aqueous dispersion of the polycarbodiimide composition was prepared in the same manner as in each example.

That is, stirrer, thermometer, a four-necked flask equipped with a reflux condenser and a nitrogen inlet tube, at room temperature, 4,4-100.0 parts by mass of dicyclohexylmethane diisocyanate _(H 12 MDI), 3- methyl - 0.5 parts by mass of 1-phenyl-2-phospholene-1-oxide (MPPO) was encapsulated. The reaction was carried out at 180 ° C. for 7 hours while introducing nitrogen to obtain a carbodiimide having isocyanate groups at both ends (carbodiimidization step).

Next, UNIOX M550 (polyoxyethylene monomethyl ether, molecular weight 550, manufactured by NOF Corporation) was added to the obtained carbodiimide in a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen inlet tube. After 86 parts by mass (0.5 equivalent with respect to both terminal isocyanates of carbodiimide) were encapsulated and reacted at 150 ° C. for 1 hour, 77 parts by mass of PEG-1000 (polyoxyethylene glycol, weight average molecular weight 1000) was added. And further reacted for 1 hour (urethane-forming step). Completion of the reaction was confirmed by infrared absorption (IR) spectrum measurement, as the absorption peak near 2260 cm ⁻¹ derived from stretching vibration of the isocyanate group almost disappeared.

Preparation of Aqueous Dispersion (Aqueous Dispersion Composition) of Polycarbodiimide Composition The obtained H ₁₂ MDI-derived polycarbodiimide composition is placed in a flask, and while being heated to 80 ° C., the resin solid content becomes 40%. Distilled water was gradually added as described above. After stirring for 5 minutes and then cooling, an aqueous dispersion of the polycarbodiimide composition was obtained.

Preparation of water-based resin composition An aqueous dispersion of the obtained polycarbodiimide composition was used as a curing agent. A hydrophilic polyurethane having a carboxyl group (polyurethane dispersion, solid content 30% by mass, solid carboxyl group equivalent 1122 g / mol) was used as the main agent, and the equivalent ratio of the carbodiimide group in the curing agent to the carboxyl group in the main agent was 0. .5 to prepare a resin composition.

<Evaluation>
・ Friction fastness test (wet)
The aqueous dispersion of the polycarbodiimide composition obtained in each of the examples and comparative examples was evaluated by a friction fastness test simulating JIS L 0849 (2013).

  More specifically, first, a liquid mixture having the following formulation was prepared.

Main agent: Takerack W-6110 (trade name, manufactured by Mitsui Chemicals): 100 parts by mass Crosslinking agent: aqueous dispersion of polycarbodiimide composition: 2 parts by mass Pigment: AF Blue E-2B (trade name, manufactured by Dainichi Seika Kogyo) : 23 parts by mass Distilled water: 75 parts by mass Next, the attached white cloth for testing (JIS L 0803 (2011) compliant, Kanakin No. 3) used in JIS L 0849 (2013) is about 220 mm in length and about 50 mm in width. It was cut into 30 mm, impregnated with the above mixture, dried overnight at room temperature, and dried at 80 ° C. for 5 minutes to obtain a test piece.

  On the other hand, an attached white cloth for testing (JIS L 0803 (2011), Kanakin No. 3) was cut into a length of about 50 mm and a width of about 50 mm, and was wetted with distilled water to obtain a friction white cloth.

  Then, the above test piece and the white cloth for friction were It was attached to a 428 Gaku shaking-type abrasion tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd., friction tester II), and rubbed under the conditions of a load of 200 g, a run-out width of 100 mm, and 100 reciprocations (30 times / min).

  The L value of the friction white cloth after the friction was measured using a spectrocolorimeter (Spectro Color Meter 2000, Nippon Denshoku Industries Co., Ltd.).

  The higher the L value, the whiter the color and the lower the degree of contamination. The L value of the friction white cloth before the test is 92.

Claims (5)

Including a polycarbodiimide composition containing a carbodiimide modified product of a reaction product of a linear aliphatic diisocyanate and an alcohol,
The alcohols include polyols and monols,
A carbodiimide crosslinking agent for treating fibers, wherein the carbodiimide equivalent of the polycarbodiimide composition is less than 550 g / mol. The carbodiimide crosslinking agent for fiber treatment according to claim 1, wherein the polyol has a molecular weight of 120 or more and 1000 or less. The carbodiimide crosslinking agent for fiber treatment according to claim 1 or 2, wherein the polyol has an average number of functional groups of 2. The carbodiimide crosslinking agent for fiber treatment according to any one of claims 1 to 3, wherein the linear aliphatic diisocyanate is 1,5-pentane diisocyanate. In the chromatogram when the polycarbodiimide composition was measured by gel permeation chromatography,
The area ratio of the peak area having a polystyrene-equivalent molecular weight of 500 or less to the total peak area is 6.5% or less,
The carbodiimide crosslinking agent for fiber treatment according to any one of claims 1 to 4, wherein an area ratio of a peak area having a molecular weight of 1,000 or less in terms of polystyrene to an entire peak area is 10.0% or less. .

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